Isocyanate-containing oligomeric polyanhydrides

ABSTRACT

Novel oligomeric poly N-carboxylic anhydrides having the following structure are disclosed.   The unit Ar represents arylene and x represents an integer from 1 to 10 and y represents a number having an average value from 0 to 4. The polyanhydrides serve as useful storage stable intermediates for the production of polyamides to which they are easily converted by the elimination of carbon dioxide. A process for the preparation of the polyanhydrides from arylene diisocyanates and Alpha , omega -alkylene dicarboxylic acids is disclosed. Processes for the conversion of the polyanhydrides to the corresponding polyamides are also disclosed.

United States Patent [191 Tilley [451 Nov. 25, 1975 l 54 l lSOCYANATE-CONTAINING OLIGOMERIC POLYANHYDRIDES [75] Inventor: James N. Tilley, Cheshire, Conn.

[73] Assignee: The Upjohn Company, Kalamazoo,

Mich.

221 Filed: Sept. 25, 1974 21 Appl. No.: 508,990

[52] US. Cl. 260/453 AR; 260/77.5 R;

260/77.5 CH; 260/77.5 AM [51] Int. Cl. C07C 119/048 [58] Field of Search 260/77.5 R, 453 AR, 453 P [56] References Cited UNITED STATES PATENTS l/l942 Gilman 260/775 X 2/1972 Allard 260/78 R Primary Examiner-Lewis Gotts Assistant ExaminerDolph H. Torrence Attorney, Agent, or FirmJames S. Rose [57] ABSTRACT Novel oligomeric poly N-carboxylic anhydrides having the following structure are disclosed.

.converted by the elimination of carbon dioxide. A

process for the preparation of the polyanhydrides from arylene diisocyanates and a,w-alkylene dicarboxylic acids is disclosed. Processes for the conversion of the polyanhydrides to the corresponding polyamides are also disclosed.

13' Claims, N0 Drawings ISOCYANATE-CONTAINING OLIGOMERIC SUMMARY OF THE INVENTION POLYANHYDRIDES This invention comprises oligomeric poly N-carboxylic anhydrides having the structure o o o o o H II II I H H H II ll OCNArN-C -o c CH )-COCN-ArNC -o-c cH-r)C0oH x y x BACKGROUND OF THE INVENTION wherein Ar represents an arylene radical, .r represents 1. Field of the Invention an integer from 1 to 10, and y represents a number hav- This invention relates to the preparation of polyaming an average value from 0 to 4 inclusive.

ides and intermediates thereto, and is more particularly The invention also comprises a process for the prepaconcerned with novel oligomeric intermediates, which ration of oligomeric poly N-carboxylic anhydrides havare readily converted to polyamides, and with the preping the structure set forth hereinabove and their conaration of said oligomeric intermediates. version to the corresponding polyamides.

2. Description of the Prior Art The term arylene represents a radical obtained by Polyamides and copolyamides of many diverse types removing two nuclear hydrogen atoms from an arohave been recognized and utilized in the polymer art matic hydrocarbon, and is inclusive of phenylene, tolylfor many years. Beginning with the pioneer work of ene, xylylene, naphthylene, diphenylylene, and com- Carothers (see US. Pat. Nos. 2,071,250, 2,071,251, pounds having the formula and 2,071,253) and continuing up to recent technology (see Encyclopedia of Polymer Sci. and Technology, R Vol. 10, pp. 347-615, 1969, John Wiley & Sons, New

York, N.Y.,) many polyamide compositions have been C disclosed. The prior art discloses a variety of methods for preparing polyamides including the melt condensation technique (see U.S. Pat. No. 3,651,022) of a diamine with a dicarboxylic acid; the amine-salt techwherein R and R each represent a moiety selected nique (see Preparative Methods of Polymer Chemistry, from the class consisting of hydrogen and lower-alkyl W. R. Sorenson, et al., p. 62, 1961, lnterscience Pub. having from 1 to 4 carbon atoms inclusive, such as lnc., New York, New York) wherein the diamine and methyl, ethyl, propyl, and butyl. diacid are prereacted to form the crystalline amine-carboxylate salt prior to polymerization; the reaction of a DETAILED DESCRIPTION OF THE INVENTION diamine with a diacid chloride (see US. Pat. No. It is an object of the present invention to prepare 3,063,966); and the reaction of a diisocyanate with a oligomeric polyla,w-dicarboxyalkylene-N,N-dicardiacid (see US. Pat. No. 3,642,715). While all the boxy (diaminoarylene) anhydrides], hereinafter called methods referred to hereinabove provide polyamides 40 poly N-carboxylic anhydrides, or PNCAs for the sake and copolyamides in good yield, purity and molecular of brevity. Kricheldorf (Die Makromolekulare Chemie weight, they do not provide for any type of prepolymer 149 (1971), l27 l33) has reported the formation of technology and the advantages to be derived there- PNCA polymers from isocyanatobenzoic acids and obfrom. served expectedly small, thermal stabilities therein.

1 have now found a novel class of oligomeric The oligomeric PNCA materials having the structure (1) are prepared according to the equation wherein Ar, x and y have the significance as defined hereinbefore. The appropriate dicarboxylic acid and diisocyanate are brought together under anhydrous [a,m-dicarboxyalkylene-N,N'-dicarboxy(diaminoaryconditions to form the oligomericstructure (l). The relene)anhydrides] which are easily prepared and storage action is carried out either in the presence or absence stable. These novel oligomers serve as prepolymers for of solvent and over a relatively broad temperature the formation of the corresponding poly or copolyarange which will be set forth in detail hereinbelow. mides by the evolution of carbon dioxide. Further, this Generally speaking, the lower temperatures are emmethod of preparing polyamides provides a technique ployed when a solvent is present which is a preferred for obtaining easily other types of polymers such as embodiment of the present invention. The diisocyanate polyurethanes, polyureas, polycarbodiimides, etc., 00- is added to a solution of the dicarboxylic acid'over a polymerized with the polyamides, which method has period of time and the PNCA product is isolated by not been available heretofore using any of the prior art standard methods known to those skilled in the art, methods. such as vacuum stripping of the solvent, or filtration, or

3 precipitation by the addition of a second solvent. When the PNCA materials are prepared in the absence of solvent, at higher reaction temperatures, it will be obvious to those skilled in the art that reaction times will be shorter than when the preparation is carried out in solvent.

Surprisingly and unexpectedly the PNCA products are characterized by having a remarkable degree of thermal stability. Illustratively, the isolated oligomeric PNCA compounds display little or no change upon heating up to 100C and only minimal changes up to 150C. In a further unexpected finding the PNCA polymers having structure (I) only form oligomers and do not form true polymers. It will be recognized by one skilled in the polymer art that an oligomer is a polymer consisting of only a few monomer units such as a dimer, trimer, tetramer, etc., and up to a limit of about repeat units. It will be further recognized that the oligomeric product obtained represents an average of a mixture of the dimer, trimer, tetramer, etc. The average number of repeat units is defined as the number average degree of polymerization (D.P.) andfor simple difunctional reactants in polycondensation polymerizations it is obtained from the expression wherein p is the extent of reaction expressed as a fraction. (see Textbook of Polymer Sci., F. W. Billmeyer, p. 265-266, 1971, John Wiley & Sons, Inc., New York, NY.)

The extent of reaction for the formation of (I) is readily determined by any suitable analytical method used for end-group ana1ysis.,A particularly suitable method is infrared analysis (see Handbook of Industrial LR. Analysis, p. 253 by R. G. White, Plenum Press, 1964, New York). It is readily apparentlfrom the formula (I) that both isocyanate (NCO) and carboxylic acid (COOl-I) end groups are present and the NCO functional absorption band at 4.4 1. is particularly suited for such analysis. The degree of polymerization of structure (I) as determined from infrared analyses for unreacted NCO is from about 2 to about 10, so that the value of y therefore will be from about 0 to about 4. The PNCA products are obtained either as free flowing powders when prepared in solvent, or as a glassy solid in the absence of solvent.

In a preferred embodiment of the present invention the proportions of diisocyanate to dicarboxylic acid are advantageously from about 1.0 mole to about 1.10 mole and preferably from about 1.0 mole to about 1.01 mole respectively. The proportions of reactants set forth above provide the PNCA oligomers having approximately equivalent end-group concentrations of free isocyanate and carboxylic acid groups. In yet another embodiment the diisocyanate is used in excess to provide an isocyanate rich oligomer- Such oligomers find particular uses and have advantages to be discussed hereinbelow. The proportions of reactants to be employed in this embodiment are advantageously from about 2 moles to about 1.0 mole and preferably from about 1.5 moles to about 1.0 mole of diisocyanate to diacid respectively.

Typical examples of the 01,! alkylenedicarboxylic acids employed in the present invention are malonic acid, succinic acid, glutaric acid, adipic acid,pimelic and preferably from about -C to about 25C. The time of reaction will vary according to the temperature and the solvent but is generally from about 10 minutes to about 6 hours and preferably from about 30minutes 4 acid, suberic acid, azelaic acid, sebacicacid, 1,11- undecanedioic acid, 1,12-dodecanedioic acid and mixtures of these. A preferred class of acids consists of:

adipic acid, pimelic acid, suberic acid, azelaic acid, se- I bacic acid, 1,1 l-undecanedioic acid, 1,12-dodecanedioic. A particularly preferred acid is azelaic acid.

The diisocyanates employed in the present invention A are compounds having the structure, Ar(NCO wherein the radical, Ar is defined hereinabove. Illustrative examples are, m-phenylenediisocyanate, phenylenediisocyanate, 1,5-naphthalenediisocyanate, biphenyl-4,4'-diisocyanate, 4,4-methylen ebis(- phenylisocyanate), 2,4-toluenediisocyanate, 2,6- toluenediisocyanate, and mixtures thereof. A-particularly preferred class consists of 4,4-methylenebis-..

and 2,6-toluenediisocya-,

together in a non-reactive polar solvent. Illustrative of such solvents'are; N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-Z-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, tetrahydrofuran, and the like. The concentration of reactants dissolved in the solvent is not critical and can vary from about 1 percent to about 40 percent by weight. A particularly 1 I I preferred group of solvents consists of Nmethylpyrj rolidone and tetrahydrofuransThe reaction tempera ture is advantageously from about C to about 50C to about 4 hours.

The extent of the oligomer formation during the course of the polymerization, whether carried out in solvent or as a melt as described hereinbefore, is easily monitored by infrared absorption analysis already de-, scribed. In addition, the final oligomeric PNCA is analyzed in like fashion.

It is yet a further object of the present invention to prepare polyamides of high molecular weighthaving I the structure (11) from the PNCA oligomers of structure (I) by heating said oligomers so as to remove car bon dioxide according to the equation Ar and .r have the significance defined hereinbefore, and 1 represents the degree of polymerization associated with high molecular weight polyamides. I

The poly N-carboxylic anhydrides having structure A (I) can be prepared either in a melt reaction or in solvent as set forth in detail hereinbefore and then converted directly to the polyamide without isolation of (1). Alternatively, the compounds of structure (I) can be isolated and later transformed, either in the pres-,

minutes to ence or absence of solvent, into the corresponding polyamide (11). Accordingly, the most preferred method will be dictated by the application, or end-use of the final polymer system. In a further embodiment, the polymerization of the PNCA to polyamide is catalyzed by the presence of a tertiary amine, where, in its most preferred embodiment, a solvent is employed thereby facilitating the separation of the final polyamide from the catalyst.

The tertiary amine catalyst employed can be any of the aliphatic, or cycloaliphatic amines normally used in processes which call for tertiary amine catalysts. Examples of such amines include: triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N- methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, and the like. A particularly preferred amine is triethylamine. The concentration of amine catalyst employed is advantageously from about 0.5 weight percent to about 100 weight percent and preferably from about 2 weight percent to about 20 weight percent based on starting PNCA.

When the PNCA is converted to polyamide in the absence of solvent, the oligomer, either in the form of a powder or a pulverized form of the glassy material, is heated at about 160C to about 325C and preferably at about 160C to about 300C for about 0.5 hour to about hours.

In a preferred embodiment the PNCA (I) is dissolved in a solvent of the type, and at a concentration as recited hereinbefore. In addition a tertiary amine of the type and in the concentration set forth above, is added whereupon the solution is heated at about 80C to about 200C, and preferably from about 90C to about 150C, for a period of time from about 2 hours to about 24 hours and preferably from about 5 hours to about hours. Purification of the polyamide is carried out by employing standard techniques of precipitation and washing known to those skilled in the polymer art. The polyamide is obtained in high yield and good molecular weight.

The various embodiments of the present invention pertaining to the formation of polyamides or copolyamides from the oligomeric PNCA materials, can be carried out in the presence of other monomers or polymer systems. The monomers or polymer systems can be either reactive with the PNCA end groups, or alternatively non-reactive. 1n the former embodiment a copolymer consisting of the polyamide and the other polymer is obtained.

In the non-reactive case a physical mixture of the two polymers is obtained. As a further example, a PNCA oligomer prepared from excess diisocyanate as referred to hereinabove is easily reacted with a urethane prepolymer having hydroxyl end-groups equivalent to the excess of isocyanate, in a solvent such as those previously described. The PNC A is then converted to polyamide according to the teachings of the present invention. The resulting block copolymer consists of polyamide blocks linked to polyurethane blocks. Similarly, an amine terminated urethane prepolymer gives rise to a copolymer having polyamide and polyurethane blocks joined by urea linkages. In like fashion a polycarbodiimide prepolymer can be copolymerized with the NCO rich oligomer in the presence of any of the carbodiimide catalysts known to those skilled in the art. After conversion the resulting copolymer consists of polycarbodiimide blocks and polyamide blocks. In yet a further adaptation of the NCO rich oligomers the PNCA can be reacted with any of the diols known to those skilled in the polyurethane art. After conversion, the polymer contains polyamide blocks joined by urethane linkages.

The oligomeric poly N-carboxylic anhydride products of the present invention find particular utility as intermediates in the preparation of polyamides or copolyamides. This aspect of their utility is particularly enchanced by the fact that, as intermediates, they provide for the formation of block copolymers consisting of polyamide blocks and other blocks such as polyurethane, polyurea, and polycarbodiimide. Thusly they provide in some cases, a means for preparing copolymers which are otherwise difficult if not impossible to obtain. As a further aspect of their utility, the oligomers of the present invention are useful in the facile in situ preparation of polyamides within another environment such as in baked-on coatings and enamels. In yet a further aspect of their utility the compounds of the present invention are useful as agents for conferring either heat resistance or fire resistance to another system by virtue of their thermal conversion to polyamides which are known to possess heat and fire resistant properties and by the evolution of non-flammable carbon dioxide. A

particularly advantageous utility in this respect is their use in intumescent coatings. Such coatings find wide application as thermal and fire resistant coatings for rocket nose cones, building panels, tanks, pipe lines and the like.

The polyamide products derived from the process of the present invention possess the well known and widely diversified uses for which polyamides are well recognized. Examples of such uses include fibers, films, moldings, castings, and extrusions which encompass a myriad of applications ranging from very small parts to very large ones. In the form of fibers, the polyamides are useful in the fabrication of curtains, carpets, tires, conveyor belts, rope, etc. As film they are useful, for example, as lining for electrical components. As castings and moldings they find use as gear wheels, electrical components parts, appliance parts, etc.

The following preparations and ,.examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the invention but are not to be construed as limiting.

EXAMPLE 1 A 100ml. three-neck flask which was thoroughly dried was equipped with a stirrer, thermometer, gas inlet tube, and an addition funnel. The flask was charged with 3.8040 g. (0.0202 mole) of azelaic acid and the reaction system maintained under a blanket of oxygenfree nitrogen in order to exclude air and atmospheric moisture. Twenty-five ml. of tetrahydrofuran was added and the azelaic acid dissolved during stirring. A solution consisting of 5.0280 g. (0.0201 mole) of 4,4- methylenebis(phenylisocyanate) dissolved in 3.6 g. of tetrahydrofuran was prepared separately and charged to the addition funnel. The diisocyanate solution was added to the flask during stirring over a period of 15 minutes at 2425C. The solution was stirred and cooled from 25C down to -40C over a period of 4 hours and remained clear and fluid. The solution was stripped under a vacuum of 20-25 mm pressure at 0C. A white solid was obtained in theoretical yield and further dried at -80C under 1 mm.

An infrared spectrum of a KBr pellet of the product displayed the absorption band at 5.57 1. for the mixed anhydride and the 4.40;; and 5.75 1. bands for the isocyanate and carboxylic acid end groups respectively.

The unreacted isocyanate was 14 percent and was determined using standard methods of IR. analysis based on the NCO band (see Handbook of Industrial LR. Analysis, p. 253 by R. G. White, Plenum Press, New York, 1964). The number average degree of polymerization as calculated from the extent of isocyanate reaction was approximately 8. The oligomeric poly N- carboxylic anhydride melted at 265-270C with frothing and corresponded to the following structure.

EXAMPLE 2 A 100 ml. three-neck flask equipped as described in Example 1 was charged with 3.8204 g. (0.0203 mole) of azelaic acid and dissolved in 25 m1. of dry N-methylpyrrolidone (NMP). The addition funnel was charged with a solution of 5.0280 g. (0.0201 mole) of 4,4- methylenebis(phenylisocyanate) dissolved in 3.7 g. of NMP. The isocyanate was added to the flask over a period of 11 minutes while the reaction mixture was cooled to 12,to 18C. No carbon dioxide evolved during the addition. Stirring was continued for 24 minutes at a reaction temperature of to 21C during which time the flask contents became viscous and a thick residue formed. Following this, a total of 0.55 ml. of triethylamine was slowly added over a 45 minute period at a temperature of -5 to 25C. No gas evolution was observed and the reaction mixture remained fluid but viscous throughout. The reaction mixture was allowed to return to ambient temperature while it was left standing overnight. The flask contents formed into a brittle glass which was easily pulverized. The infrared scan of this material showed the characteristic mixed anhydride absorption around 5.6;/..

The pulverized material, which contained the NMP, was then heated and stirred for a period of about 13 hours at a pot temperature of 90-140C. The flask contents began to agglomerate and eventually became gelatinous. A solid was precipitated by stirring the product into 800 ml. of water. It was washed with two 400 ml. portions of water, followed by two 250 ml. portions of methanol. It was dried overnight at 140C under 0.5 mm. pressure and provided 5.95 g. (84.5% yield) of po1y[4,4-methylenebis (phenyl) azelamide]; 'vinh(0.5% in H 50 1.2; infrared spectrum identical to authentic polyamide.*

*Prepared from reaction of4.4'-methylenediani1ine with azeluoyl chloride in solution. See Condensation Polymers." Chapter IV by P. W. Morgan. 1965. lnterscience Publishers. New York.

EXAMPLE 3 A sample of the oligomeric poly N-carboxylic anhydride (PNCA) as prepared in Example 1 was converted to poly[4,4-methylenebis(phenyl)azelamide] by heating in a duPont 900. Thermal Analyzer instrument equipped with the duPont Thermal Gravimetric Analysis (TGA) 950 Unit.

A differential thermal analysis (DTA) scan was determined for the oligomer using the duPont 900 Thermal Analyzer instrument, under N at a rate of 20 deg/- min. The sample was cooled and rerun at the same rate. Comparative DTA scans were also obtainedfor virgin authentic poly[4,4'-methy1enebis(phenyl)azelamide] and on the cooled and rerun sample. The correspondence of the thermal events in the scans between the polyamide formed from PNCA as it was heated during the DTA scan and authentic polyamide is set forth in Table l. The profiles of heated or annealed samples were characterized by having more complicated thermal events occurring during heating.

TABLE I DTA Comparison of Polyl4,4'-methylenebis(phenyl)azelamide] with Authentic Polymer.

Authentic* Sample Polyamide m.p. (C) 250-280 1 250-280 Virgin Polymer Cool (recryst.) (C) 245 235 Endothermic Annealed Event (C) 230-245 225-255 or heat treated Exothermic polymer Event (C) 245-250 255-260 m.p. (C) 260-275 270-285 The identical complex DTA pattern for polyl4,4'-methylenebis(phenyl)azelamide] has been observed by D. A. Holmer. e! AL. .1. Polymer Scil511547 (1972).

Tablell sets forth the weight loss of the polyanhydride during its conversion to polyamide and the corre sponding percent conversion thereto. The theoretical. weight loss due to CO evolution when the polyanhydride has been completely converted to polyamide is 20.1%. The sample was heated at 15C .per minute under nitrogen and the instrument suppression was varied so that the maximum sensitivity was at the beginning of the heating cycle when weight loss was smallest.

Table 111 sets forth a comparison of the TGA of a sample of the polyamide after its formation and continued heating, with the TGA of authentic polyamide and the correspondence between the two samples is evident. The discrepancy in the 450 to 500C range isconsidered an artifact.

TABLE 11 Wt. Loss During Thermal Conversion of PNCA to Polyamide. 5

TABLE Ill TGA Comparison of Formed Polyamide with Authentic Polymer.

Wt. Loss (71) Temp. (C) Polyamide Authentic Material EXAMPLE 4 A small polypropylene beaker wascharged with 15 1 1.4120 g. (0.0607 mole) of azelaic acid, and 2.0898 g. (0.0120 mole) of 2,4-tluene diisocyanate. The beaker and contents were preheated (while covered) for minutes in an oven at 95 100C. Thereupon 12.0672 g. (0.0482 mole) 4,4'-methylenebis(phenylisocyanate) was weighed in and a semi-micro resin kettle top quickly affixed to the beaker. The top was equipped with a mechanical stirrer and a thermocouple for continuous temperature mea surement within the reaction mixture. The beaker was suspended in an oil bath and heated and stirred at a bath temperature of 100C. The reaction mixture was held for 5 /2 minutes at a mix temperature of 95C whereupon a water-white homogeneous phase was formed which foamed slightly then collapsed to a gel. It was cooled to form a glassy blend and the infrared analysis displayed the typical mixed anhydride pattern with the 5.6; absorption which characterizes the poly N- carboxylic anhydride structure, in combination with the isocyanate and carboxylic acid end group absorptions at 4.40/1. and 5.80;]. respectively. The following data sets forth the TGA analysis of the product and the equivalent percent conversion to the corresponding copoly[4,4'-methylenebis(phenyl)2,4-tolyl azelamide] as the material was heated (assuming theoretical wt. loss due to CO evolution as 20.1%. After approximately 400C the wt. loss was due to thermal degradation of the formed copolyamide.

Copolyamide v300 v l 350 l 400 l 450 500 The polyamide obtained had the following structure o o AHLL LN 2 wherein percent of the radicals Ar were -and the remaining 20 percent were EXAMPLES 5 10 The PNCA oligomers set forth in the following Table IV were prepared using the apparatus and procedure set forth in Example 1. The 0.0202 mole of azelaic acid and 0.0201 mole of 4,4-methylenebis(phenylisocyanate) of Example 1 were replaced by the equivalent amounts of a,m-alkylenedicarboxylic acids and diisocyanate as indicated hereinbelow. The oligomers had the following structure 0 O O O Ol TA LE 'IV PNCA oligomers g l Diacid Diisocyanate 5 Ar I.R. Analysis 5 succinic 4,4-methylenebis 2 5.6u (mixed anhydride) (phenylisocyanate) 6 adipic 4,4-methylenebis (phenylisocyanate) 4 Q Q 5.6 (mixed anhydride) 7 sebacic 4,4-methylenebis (phenylisocyanate) 8 5' 5.6 (mixed anhydride) 8 l l2-dodecanedioic 4,4-methylenebis (phenylisocyanate) l0 =T 5 6 (mixed anhydride) cn 9 adipic 2,4toluened11socyanate 4 @j/ 3 5,6 (mixed anhydride) l0 l,l2dodecanedioic 2,4-toluenediisocyanate l0 5.6 (mixed anhydride) The oligomers were converted to the corresponding polyamides using the procedure set forth in Example 2. The N-methylpyrrolidone semi-solid solutions (about 25 percent by weight of PNCA) of each oligomer were heated at 125C for 12 hours. The corresponding polyamides were obtained by precipitation into 800 ml. of water, collected and washed with two 400 ml. portions of water, followed by two 250 ml. portions of methanol. The polyamides were dried overnight at 140C under 0.5 mm pressure to yield light cream colored powders. The infrared absorption spectrum of each polyamide was identical to the spectrum of the authentic polymer.

1 claim: 1 1. An oligomeric poly N-carboxylic anhydride having the structure 0 ll ll wherein Ar represents an arylene radical selected from the group consisting of'phenylene, tolylene, Xylylene,

naphthylene, diphenylylene, and compounds having 2. A poly N-carboxylic anhydride according to claim 1 wherein Ar represents 3. A poly N-carboxylic anhydride according to claim 1 wherein 80 percent of said arylene radicals are group consisting of H a CH and mixtures thereof. 4

4. A poly N-carboxylic anhydride according to claim 1 wherein x is equal to 7.

5. A poly N-carboxylic anhydride according 1 wherein y is equal to 3.

to claim 6. A process for the. preparation of an oligomeric A poly N-carboxylic anhydride according to claim 1 said process comprising reacting under anhydrouscondi tions an arylene diisocyanate selected from the. group consisting of phenylene diisocyanate. tolylene diisocya nate, Xylylene diisocyanate, naphthylene diisocyanate,

diphenylylene diisocyanate, and diisocyanates having the formula OCN wherein R, and R each represent a moiety selected" from the class consisting of hydrogen and lower alkyl having from one to four carbon atoms inclusive and 'an a, m-alkylenedicarboxylic acid.

7. A process according to claim 6 wherein said diiso cyanate is 4,4'-methylenebis( phenylisocyanate).

of 2,4-toluene diisocyanate.

9. A process according to claim 6 wherein said dicar boxylic acid is azelaic acid.

10. A process according to claim 6 wherein said diisocyanate and said dicarboxylic acid are brought together in the absence of solvent at a temperature of t from about C to about C.

11. A process according to claim 6 wherein said di-" isocyanate and said dicarboxylic acid are brought together in the presence of a polar solvent ata tempera:-

tureof from about 60C to about 50C.

12. A process according to claim 11 wherein said solvent is tetrahydrofuran.

13. A process according to claim 11 wherein said 501- vent is N-methylpyrrolidone.

UNITED STATES PATENT OFFICE CERTIFlCATE 0F CORRECTION Patent 3,922, 295 Dated November 25, 1975 a Inventor) James N. Tllley It is eel-t1 Eied that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 6 Column 1, line 58: Should read:

[01,, w-dicarboxyalkylenepoly [0a,w-diearboxyalkylene- Column 4, line 8: Should read: 0

Ar (NCO A (NC 2 Column 7, line 59: Should read:

inh(0.5% in H SO inh(0.5% in H SO 0 Column 10, lines 45 to 50: Should read= (CH COOH (on COOH Column 11,, claim l, line .19: Should read: H 9 9 OCN-Ar-N C-O- OCl\TArN-C O- a Signed and Scaled this Tenth Day of August 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'latenrs and Trademarks 

1. AN OLIGOMERIC POLY N-CARBOXYLIC ANHYDRIDE HAVING THE STRUCTURE
 2. A poly N-carboxylic anhydride according to claim 1 wherein Ar represents
 3. A poly N-carboxylic anhydride according to claim 1 wherein 80 percent of said arylene radicals are
 4. A poly N-carboxylic anhydride according to claim 1 wherein x is equal to
 7. 5. A poly N-carboxylic anhydride according to claim 1 wherein y is equal to
 3. 6. A process for the preparation of an oligomeric poly N-carboxylic anhydride according to claim 1 said process comprising reacting under anhydrous conditions an arylene diisocyanate selected from the group consisting of phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylylene diisocyanate, and diisocyanates having the formula
 7. A process according to claim 6 wherein said diisocyanate is 4,4''-methylenebis(phenylisocyanate).
 8. A process according to claim 6 wherein said diisocyanate comprises a mixture of 80 mole percent 4,4''-methylenebis(phenylisocyanate) and 20 mole percent of 2,4-toluene diisocyanate.
 9. A process according to claim 6 wherein said dicarboxylic acid is azelaic acid.
 10. A process according to claim 6 wherein said diisocyanate and said dicarboxylic acid are brought together in the absence of solvent at a temperature of from about 80*C to about 150*C.
 11. A process according to claim 6 wherein said diisocyanate and said dicarboxylic acid are brought together in the presence of a polar solvent at a temperature of from about -60*C to about 50*C.
 12. A process according to claim 11 wherein said solvent is tetrahydrofuran.
 13. A process according to claim 11 wherein said solvent is N-methylpyrrolidone. 